CN104159938A - Polymer, composition containing said polymer, and single-layer-coated horizontally oriented film - Google Patents

Polymer, composition containing said polymer, and single-layer-coated horizontally oriented film Download PDF

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CN104159938A
CN104159938A CN201380013090.1A CN201380013090A CN104159938A CN 104159938 A CN104159938 A CN 104159938A CN 201380013090 A CN201380013090 A CN 201380013090A CN 104159938 A CN104159938 A CN 104159938A
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polymkeric substance
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methyl
film
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CN104159938B (en
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丹尼尔·安东尼奥·樱叶汀
汤川升志郎
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Nissan Chemical Corp
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    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
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    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
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    • G02—OPTICS
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    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
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    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
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Abstract

A polymer characterized by containing repeating units respectively represented by formulae [1a], [1b] and [1c]. The polymer enables the production of a single-layer-coated horizontally oriented film by a simple process. [In the formulae, X and Y independently represent a group represented by formula [2] or [3]; M1 and M2 respectively represent a group represented by formula [4] and a group represented by formula [5]; A represents a linear or branched alkyl group having 2 to 15 carbon atoms; m, n and p represent numeral values fulfilling the formulae 0 < m < 1, 0 < n < 1, 0 <= p <= 0.5 and m+n+p <= 1; and q and r independently represent an integer of 2 to 9.] .

Description

Polymkeric substance, the composition that contains this polymkeric substance and single coating type horizontal alignment film
Technical field
The composition that the present invention relates to polymkeric substance, contains this polymkeric substance and single coating type horizontal alignment film.Particularly, relate to and can preferably be used in liquid-crystalline polymer, the composition that contains this polymkeric substance of the optical compensation films such as Polarizer that material, the particularly liquid-crystal display of the optical characteristics with purposes such as being suitable for display unit or recording materials use and polarizer and the single coating type horizontal alignment film being obtained by said composition.
Background technology
For the requirement that improves the demonstration grade of liquid crystal indicator and lightweight etc., the optical compensation films as Polarizer or polarizer etc., increases day by day to having controlled the requirement of the polymeric membrane of inner Molecular orientational structure.In order to tackle this requirement, developed the optically anisotropic film that utilizes polymerizable liquid crystal compound to have.
Polymerizable liquid crystal compound is generally the liquid crystalline cpd with polymerizable group group and liquid crystal structure position (structure position with interval parts and mesomorphic portion) as used herein, as this polymerizable group group, is widely used acrylic.
This polymerizable liquid crystal compound is generally that the method for carrying out polymerization by irradiation ultraviolet radiation isoradial is made polymkeric substance (film).
For example, known the specific aggregation liquid crystalline cpd with acrylic is carried between supporter, on one side this compound is remained on to mesomorphic state, irradiates the method (patent documentation 1) that radioactive rays obtain polymkeric substance on one side; And in the mixture of 2 kinds of polymerizable liquid crystal compounds with acrylic or be mixed with in this mixture in the composition of chiral liquid crystal and add Photoepolymerizationinitiater initiater, irradiation ultraviolet radiation obtains the method (patent documentation 2) of polymkeric substance.
In addition, there is bibliographical information, do not need liquid crystal orientation film and use the alignment films (patent documentation 3,4) of polymerizable liquid crystal compound or polymkeric substance or use the various single coating type alignment films such as alignment films (patent documentation 5,6) of the polymkeric substance contain photo-crosslinking position.But above-mentioned film production technique exists the solvability of polymkeric substance low, must use the problems such as solvent of the solvency power excellences such as NMP, chloroform, chlorobenzene as the solvent of the polymkeric substance using, do not find at present the material that can address this is that.
Prior art document
Patent documentation
Patent documentation 1: Japanese kokai publication sho 62-70407 communique
Patent documentation 2: Japanese kokai publication hei 9-208957 communique
Patent documentation 3: european patent application discloses specification sheets No. 1090325
Patent documentation 4: No. 2008/031243rd, International Publication
Patent documentation 5: TOHKEMY 2008-164925 communique
Patent documentation 6: Japanese kokai publication hei 11-189665 communique
Summary of the invention
The problem that invention will solve
The present invention is formally in view of above-mentioned problem completes, its object is, a kind of single coating type horizontal alignment film that can be produced the new polymkeric substance of single coating type horizontal alignment film, the composition that contains this polymkeric substance and be obtained by said composition by simple technique is provided.
Solve the means of problem
The inventor etc. are further investigation repeatedly in order to solve above-mentioned problem, found that, by using main chain to contain gamma-butyrolactone skeleton, and in the γ position by lactonic ring, play the polymkeric substance on the side chain of extension with laurate structure, may be owing to having formed stable reticulated structure after polarisation ultraviolet exposure, therefore, can obtain thering is high refractive index anisotropy in the situation that the not using liquid crystal orientation film horizontal alignment film of (Δ n), and then, by import alkyl chain in this polymkeric substance, can under cold condition, make the solvability of organic solvent is improved, and the horizontal alignment film with higher Δ n, so far completed the present invention.
That is, the invention provides:
1, a polymkeric substance, is characterized in that, the repeating unit that contains following formula [1a], [1b] and [1c] expression,
[changing 1]
[in formula, X and Y are the group that following formula [2] or [3] represent independently of one another,
[changing 2]
(in formula [3], R 1for hydrogen atom or methyl, dotted line is key)
M 1for the group that following formula [4] represents, M 2for the group of following formula [5] expression,
[changing 3]
(in formula [4] and [5], s1, s2, s3 and s4 are 1 or 2, G independently of one another 1and G 2be independently of one another singly-bound ,-COO-or-OCO-, R 2and R 3be the alkyl of hydrogen atom, halogen atom, cyano group, carbon number 1～10 or the alkoxyl group of carbon number 1～10 independently of one another, dotted line is key),
A is the straight or branched alkyl of carbon number 2～15,
M, n and p are respectively and meet 0<m<1,0<n<1,0≤p≤0.5, and the number of m+n+p≤1,
Q and r are 2～9 integer independently of one another].
2, the polymkeric substance as described in 1, wherein, above-mentioned X and Y are the group that above-mentioned formula [3] represents.
3, the polymkeric substance as described in 1 or 2, wherein, above-mentioned m, n and p are respectively the number that meets 0.2≤m≤0.9,0.1≤n≤0.8,0≤p≤0.4.
4, the polymkeric substance as described in 3, wherein, above-mentioned m, n and p are respectively the number that meets 0.2≤m≤0.8,0.1≤n≤0.5,0.1≤p≤0.3.
5, composition, it contains polymkeric substance and organic solvent described in 1～4 any one.
6, single coating type horizontal alignment film, it is by the composition described in 5 is coated to substrate, then irradiates polarisation and makes its curing obtaining.
7, the single coating type horizontal alignment film as described in 6, wherein, above-mentioned polarisation is linear polarization ultraviolet ray.
8, optics, it possesses the single coating type horizontal alignment film described in 6 or 7.
9, polymerizable compound, is characterized in that, by following formula [7], represented,
[changing 4]
(in formula [7], s3 and s4 are 1 or 2, G independently of one another 2for singly-bound ,-COO-or-OCO-, R 3for the alkyl of hydrogen atom, halogen atom, cyano group, carbon number 1～10 or the alkoxyl group of carbon number 1～10).
Invention effect
Polymkeric substance of the present invention contains gamma-butyrolactone skeleton at main chain.Therefore, the composition that contains this polymkeric substance by coating, and the technique of at room temperature irradiating linear polarization and carrying out rear baking, can make the single coating type horizontal alignment film that demonstrates high Δ n.In addition, further, by making the polymkeric substance that contains the unit with alkyl group side chain, can improve the solvability to solvent.
Accompanying drawing explanation
Fig. 1 means that each film of being obtained by embodiment 11～16 is at the figure of the length of delay dependence of angle at wavelength 550nm place.
Fig. 2 means that each film of being obtained by comparative example 3,4 is at the figure of the length of delay dependence of angle at wavelength 550nm place.
Embodiment
Below, illustrate in greater detail the present invention.
[polymkeric substance]
The repeating unit that polymkeric substance of the present invention contains following formula [1a] and [1b] expression, as required, can also contain the repeating unit that following formula [1c] represents.
[changing 5]
In formula [1a] and [1c], X and Y are the group that following formula [2] or [3] represent independently of one another.
[changing 6]
(in formula [3], R 1for hydrogen atom or methyl, dotted line is key (lower same)),
Wherein, X, Y are all preferably the group that formula [3] represents.
In formula [1a], M 1for the group of following formula [4] expression, in formula [1b], M 2group for following formula [5] expression.
[changing 7]
(in formula [4] and [5], s1, s2, s3 and s4 are 1 or 2, G independently of one another 1and G 2be independently of one another singly-bound ,-COO-or-OCO-, R 2and R 3be the alkyl of hydrogen atom, halogen atom, cyano group, carbon number 1～10 or the alkoxyl group of carbon number 1～10 independently of one another).
At this, as above-mentioned halogen atom, can enumerate fluorine, chlorine, bromine, iodine atom, in the present invention, preferred fluorine atom.
As abovementioned alkyl, can be any of straight chain, side chain, ring-type, in addition, its carbon number is also not particularly limited, but in the present invention, is preferably the alkyl of the carbon number 1～10 of straight chain.As the concrete example of abovementioned alkyl, can enumerate methyl, ethyl, n-propyl, sec.-propyl, cyclopropyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, cyclobutyl, n-pentyl, cyclopentyl, n-hexyl, cyclohexyl, n-heptyl, n-octyl, n-nonyl, positive decyl etc.Wherein, more preferably the alkyl of carbon number 1～3, is particularly preferably methyl, ethyl etc.
As above-mentioned alkoxyl group, can be any of straight chain, side chain, ring-type, in addition, its carbon number is not particularly limited, and in the present invention, is preferably the alkoxyl group of the carbon number 1～10 of straight chain.As the concrete example of above-mentioned alkoxyl group, can enumerate methoxyl group, oxyethyl group, positive propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert.-butoxy, n-pentyloxy, positive hexyloxy, positive heptan oxygen base, n-octyloxy, positive ninth of the ten Heavenly Stems oxygen base, n-decyloxy etc.Wherein, more preferably the alkoxyl group of carbon number 1～3, is particularly preferably methoxyl group, oxyethyl group etc.
Be explained, in abovementioned alkyl, alkoxyl group, partly or entirely hydrogen atom can be replaced by halogen atoms such as fluorine atoms.
As above-mentioned R 2or R 3, be preferably hydrogen atom, fluorine atom, cyano group, methyl, methoxyl group.
As above-mentioned G 1, be preferably-COO-or-OCO-, as G 2, be preferably singly-bound.
In formula [1c], the alkyl of the carbon number 2～15 that A is straight or branched.As abovementioned alkyl, specifically can enumerate ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, n-pentyl, 1-methyl normal-butyl, 2-methyl normal-butyl, 3-methyl normal-butyl, 1,1-dimethyl n propyl group, 1,2-dimethyl n propyl group, 2,2-dimethyl n propyl group, 1-ethyl n-propyl, n-hexyl, 1-methyl n-pentyl, 2-methyl n-pentyl, 3-methyl n-pentyl, 4-methyl n-pentyl, 1,1-dimethyl n butyl, 1,2-dimethyl n butyl, 1,3-dimethyl n butyl, 2,2-dimethyl n butyl, 2,3-dimethyl n butyl, 3,3-dimethyl n butyl, 1-ethyl normal-butyl, 2-ethyl normal-butyl, 1,1,2-trimethylammonium n-propyl, 1,2,2-trimethylammonium n-propyl, 1-ethyl-1-methyl n-propyl, 1-Ethyl-2-Methyl n-propyl, n-heptyl, 1-methyl n-hexyl, 2-methyl n-hexyl, 3-methyl n-hexyl, 1,1-dimethyl n amyl group, 1,2-dimethyl n amyl group, 1,3-dimethyl n amyl group, 2,2-dimethyl n amyl group, 2,3-dimethyl n amyl group, 3,3-dimethyl n amyl group, 1-ethyl n-pentyl, 2-ethyl n-pentyl, 3-ethyl n-pentyl, 1-methyl isophthalic acid-ethyl normal-butyl, 1-methyl-2-ethyl normal-butyl, 1-Ethyl-2-Methyl normal-butyl, 2-methyl-2-ethyl normal-butyl, 2-ethyl-3-methyl normal-butyl, n-octyl, 1-methyl n-heptyl, 2-methyl n-heptyl, 3-methyl n-heptyl, 1,1-dimethyl n hexyl, 1,2-dimethyl n hexyl, 1,3-dimethyl n hexyl, 2,2-dimethyl n hexyl, 2,3-dimethyl n hexyl, 3,3-dimethyl n hexyl, 1-ethyl n-hexyl, 2-ethyl n-hexyl, 3-ethyl n-hexyl, 1-methyl isophthalic acid-ethyl n-pentyl, 1-methyl-2-ethyl n-pentyl, 1-methyl-3-ethyl n-pentyl, 2-methyl-2-ethyl n-pentyl, 2-methyl-3-ethyl n-pentyl, 3-methyl-3-ethyl n-pentyl, n-nonyl, positive decyl, n-undecane base, dodecyl, n-tridecane base, n-tetradecane base, Pentadecane base etc.
Wherein, when considering resulting polymers to the solvability of organic solvent etc., preferably carbon number 4～15, particularly preferably 4～12 alkyl, more preferably normal-butyl, 2-ethyl n-hexyl, dodecyl etc.
In formula [1a]～[1c], m, n and p are respectively and meet 0<m<1,0<n<1,0≤p≤0.5, and the number of m+n+p≤1.From the viewpoint considerations such as solvability that improve Δ n or improve polymkeric substance, m, n and p are preferably respectively the number that meets 0.2≤m≤0.9,0.1≤n≤0.8,0≤p≤0.4, are more preferably respectively the number that meets 0.2≤m≤0.8,0.1≤n≤0.5,0.1≤p≤0.3.
In addition, in formula [1a] and [1b], q and r are 2～9 integer independently of one another, but be preferably 3～6, q, are particularly preferably 5 or 6.
[polymerizable compound]
Polymerizable compound as the raw material of polymkeric substance of the present invention is represented by following formula [6], [7] or [8].
[changing 8]
[in formula, R 2, R 3, G 1, G 2, A, q, r and s1～s4 definition same as described above.
X' and Y' are the polymerizable group that following formula [9] or [10] represent independently of one another.
[changing 9]
(in formula, R 1definition same as described above)].
[synthesizing of polymerizable compound]
The polymerizable compound that above-mentioned formula [6] represents for example can be produced as follows.
At G 1in situation for-COO-, as shown in following flow diagram, can manufacture by making benzoic acid derivative that formula [12] represents and amphyl carry out condensation in solvent, under the existence of condensing agent.
[changing 10]
(in formula, R 2, X', q, s1 and s2 definition same as described above.DCC represents N, N'-dicyclohexylcarbodiimide, DMAP represents 4-dimethylaminopyridine).
At G 1in situation for-OCO-, as shown in following flow diagram, can manufacture by making amphyl that formula [13] represents carry out condensation with benzoic acid derivative in solvent, under the existence of condensing agent.
[changing 11]
(in formula, R 2, X', q, s1 and s2 definition same as described above).
The compound that above-mentioned formula [12] and [13] represent, in the situation that X' is the group that formula [9] represents, can be buied as the commercially available product of SYNTHON Chemicals company or Midori KCC.
In addition, the compound that above-mentioned formula [12] and [13] represent, in the situation that X' is the group that formula [10] represents, can be used such as (P.Talaga such as Talaga, M.Schaeffer, C.Benezra and J.L.Stampf, Synthesis, 530 (1990)) method of proposing synthesizes.The method, as shown in following synthetic schemes (A1), is used SnCl 2the method that 2-(brooethyl) vinylformic acid is reacted with aldehydes or ketones.Be explained, 2-(brooethyl) vinylformic acid can obtain by the method for the proposals such as Ramarajan (K.Ramarajan, K.Kamalingam, D.J.O'Donnell and K.D.Berlin, Organic Synthesis, vol.61, pp.56-59 (1983)).
[changing 12]
(in formula, R' represents any monovalent organic radical group, and Amberlyst (registered trademark) 15 is the ion exchange resin of Rohm and Haas company system, and THF represents tetrahydrofuran (THF), and Et represents ethyl).
In addition, using SnCl 2the acrylic acid reaction of 2-(brooethyl) in, also can, by replacing aldehydes or ketones to react with corresponding acetal or ketal, obtain thus alpha-methylene-gamma-butyrolactone structure.
As acetal or ketal, can enumerate there is dimethylacetal base, diethyl acetal base, 1, the compound of 3-alkyl dioxin, DOX base etc.Synthetic method and protecting group when following synthetic schemes (A2) represents to use acetal or ketal.
[changing 13]
(in formula, the definition of R' is same as described above).
By applying following synthetic schemes (B) or the method (C) of above-mentioned synthetic schemes (A1) or method (A2), can synthesize the compound that formula [12] or [13] represent.
[changing 14]
(in formula, the definition of q and s1 is same as described above, and Me represents methyl, and PCC represents pyridinium chloro-chromate),
[changing 15]
(in formula, the definition of q and s1 is same as described above).
The compound that formula [7] represents, for example, as shown in following flow diagram, can be by making compound that formula [14] represents and Cinnamic acid compounds in solvent, condensation is manufactured under the existence of condensing agent.
[changing 16]
(in formula, R 3, G 2, r, s3 and s4 definition same as described above).
The compound that formula [14] represents can obtain by for example method shown in following synthetic schemes (D).
[changing 17]
(in formula, G 2, r, s3 and s4 definition same as described above).
The compound that formula [8] represents, in the situation that Y' is the group that formula [9] represents, can be buied as commercially available product.
In addition, the compound that formula [8] represents, in the situation that Y' is the group that formula [10] represents, also can synthesize by the method shown in following synthetic schemes (E).
[changing 18]
(in formula, the definition of A is same as described above).
[synthesizing of polymkeric substance]
Method as synthetic polymkeric substance of the present invention, is not particularly limited, and can adopt radical polymerization, anionoid polymerization, cationoid polymerisation etc.Wherein, particularly preferably radical polymerization, particularly, as long as above-mentioned polymerizable compound heating is made to its polymerization in solvent, under the existence of polymerization starter.
As above-mentioned polymerization starter, can use from suitable selection known polymerization starter in the past.Such as enumerating the superoxide such as benzoyl peroxide, cumyl hydroperoxide, tertbutyl peroxide; The persulphates such as Sodium Persulfate, Potassium Persulphate, ammonium persulphate; The azo based compounds such as azobis isobutyronitrile (AIBN), the two methylbutyronitriles of azo, the two isovaleronitriles of azo etc.They may be used alone or in combination of two or more kinds.
The usage quantity of above-mentioned polymerization starter is preferably 0.01～0.05mol left and right with respect to polymerizable compound 1mol.
Temperature of reaction needs only and is suitably set in 0 ℃ to the boiling point of the solvent using, but is preferably 20～100 ℃ of left and right.Reaction times was preferably about 0.1～30 hour.
The solvent using as polyreaction, is not particularly limited, as long as the suitable choice for use of all kinds of SOLVENTS generally using in above-mentioned polyreaction.Specifically can enumerate: water; The alcohols such as methyl alcohol, ethanol, 1-propyl alcohol, 2-propyl alcohol, n-butyl alcohol, 2-butanols, isopropylcarbinol, the trimethyl carbinol, 1-amylalcohol, 2-amylalcohol, 3-amylalcohol, primary isoamyl alcohol, tertiary amyl alcohol, 1-hexanol, 1-heptanol, 2-enanthol, 3-enanthol, sec-n-octyl alcohol, 2-ethyl-1-hexanol, benzylalcohol, hexalin; The ethers such as ether, Di Iso Propyl Ether, dibutyl ether, cyclopentyl-methyl ether, tetrahydrofuran (THF), Isosorbide-5-Nitrae-dioxs; The halogenated hydrocarbons such as chloroform, methylene dichloride, ethylene dichloride, tetracol phenixin; The ether alcohol classes such as methylcyclohexane, ethyl cellosolve, ispropyl cellosolve, ethylene glycol butyl ether, diglycol monotertiary butyl ether; The ketones such as acetone, butanone, methyl iso-butyl ketone (MIBK), pimelinketone; The ester classes such as ethyl acetate, butylacetate, ethyl propionate, cellosolve acetic ester; Aliphatic series or the aromatic hydrocarbons such as Skellysolve A, normal hexane, normal heptane, octane, positive nonane, n-decane, pentamethylene, methylcyclopentane, hexanaphthene, methylcyclohexane, benzene,toluene,xylene, ethylbenzene, methyl-phenoxide; The acetals such as methylal, acetal; The fatty acids such as formic acid, acetic acid, propionic acid; Nitropropane, oil of mirbane, dimethylamine, monoethanolamine, pyridine, METHYLPYRROLIDONE (NMP), DMF, methyl-sulphoxide, acetonitrile etc.They can be used alone a kind or mix two or more use.
The weight-average molecular weight of polymkeric substance of the present invention is preferably 3,000～200, and 000, more preferably 4,000～150,000, more preferably 5,000～100,000.If weight-average molecular weight surpasses 200,000, sometimes the decreased solubility of solvent, operability are reduced, not enough if weight-average molecular weight, lower than 3,000, is solidified during thermofixation sometimes, solvent patience and thermotolerance reduce.
Be explained the polystyrene conversion measured value of weight-average molecular weight for utilizing gel permeation chromatography (GPC) to record.
In addition, polymkeric substance of the present invention only otherwise damage effect of the present invention, can also contain above-mentioned formula [1a]～[1c] other repeating unit in addition.As the polymerizable compound of giving above-mentioned other repeating unit, can enumerate acrylic compound, methacrylate compound, maleimide compound, acrylamide compound, vinyl cyanide, maleic anhydride, distyryl compound etc.
The containing ratio of above-mentioned other repeating unit is preferably 0～10 % by mole with respect to 100 % by mole of total repeating units.If the containing ratio of above-mentioned other repeating unit is too high, the characteristic of polymkeric substance of the present invention reduces, and such as characteristics such as liquid crystal liquid crystal property, declines sometimes.
In the situation that polymkeric substance of the present invention contains above-mentioned other repeating unit, as its synthetic method, as long as make the polymerizable compound of giving above-mentioned other repeating unit coexist and carry out polymerization when above-mentioned polymerization.
Be explained, polymkeric substance of the present invention can be any of randomcopolymer, alternating copolymer, segmented copolymer.
[composition]
Composition of the present invention is by being obtained by mixing with organic solvent at least a kind of above-mentioned polymkeric substance.
As above-mentioned organic solvent, such as enumerating the ethers such as tetrahydrofuran (THF), diox; The aromatic hydrocarbons such as benzene,toluene,xylene; DMF, METHYLPYRROLIDONE isopolarity solvent; The ester classes such as ethyl acetate, butylacetate, ethyl lactate; The alkoxy ester classes such as 3-methoxy methyl propionate, 2-methoxy methyl propionate, 3-methoxy propyl acetoacetic ester, 2-methoxy propyl acetoacetic ester, 3-ethoxyl ethyl propionate, 2-ethoxyl ethyl propionate; The glycol dialkyl ethers such as ethylene glycol dimethyl ether, propylene glycol dimethyl ether; The glycol ether dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, glycol ether methyl ethyl ether, dipropylene glycol dimethyl ether; The glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether; The monoalkyl ethers of diethylene glycol classes such as diglycol monotertiary methyl ether, carbiphene, DPGME, dihydroxypropane single-ethyl ether; The glycol monoalkyl ether ester classes such as propylene glycol monomethyl ether, Trivalin SF acetic ester, ethyl cellosolve acetate; The ketones such as pimelinketone, butanone, methyl iso-butyl ketone (MIBK), 2-heptanone.These organic solvents can be used alone or combine two or more uses.
Wherein, preferred propylene glycol monomethyl ether, propylene glycol monomethyl ether, ethyl lactate, pimelinketone etc.
The usage quantity of organic solvent is suitably for and in composition, accounts for 60～95 quality % left and right.
In addition, in order to improve the affinity with substrate, in composition of the present invention, can also add tensio-active agent.As tensio-active agent, be not particularly limited, can enumerate fluorine and be tensio-active agent, silicon-type tensio-active agent, nonionic is tensio-active agent etc., but preferably and the affinity of substrate to improve the fluorine that effect is high be tensio-active agent.
It as fluorine, is the concrete example of tensio-active agent, can enumerate (below for trade(brand)name) エ Off ト ッ プ EF301, EF303, EF352 ((strain) ト ー ケ system プ ロ ダ Network Star system), メ ガ Off ァ ッ Network F171, F173, R-30 (DIC (strain) system), Off ロ ラ ー De FC430, FC431 (Sumitomo 3M (strain) system), ア サ ヒ ガ ー De AG710, サ ー Off ロ Application S-382, SC101, SC102, SC103, SC104, SC105, SC106 (Asahi Glass (strain) system) etc., but be not limited thereto.Be explained, tensio-active agent can be used alone or combines multiple use, and its addition is preferably below 5 mass parts with respect to polymkeric substance 100 mass parts.
And then, in order to improve the adaptation with substrate, in composition of the present invention, can also add closely sealed promotor.
As closely sealed promotor, can enumerate the chlorosilane classes such as trimethylchlorosilane, dimethyl vinyl chlorosilane, methyldiphenyl base chlorosilane, CMDMCS chloromethyl dimethyl chlorosilane; The alkoxyl silicone alkanes such as trimethylammonium methoxy silane, dimethyldiethoxysilane, methyl dimethoxysilane, Vinyldimethylethoxysilane, dimethoxydiphenylsilane, phenyl triethoxysilane; Hexamethyldisilazane, N, the silazane classes such as two (TMS) ureas of N'-, dimethyl trimethyl silyl amine, trimethyl-silyl-imidazole: vinyl trichloro silane, γ-r-chloropropyl trimethoxyl silane, γ aminopropyltriethoxy silane, γ-methacryloxypropyl trimethoxy silane, γ-glycidoxypropyltrimewasxysilane, γ-silicane such as (N-piperidyl) propyl trimethoxy silicane; The assorted ring compounds such as benzotriazole, benzoglyoxaline, indazole, imidazoles, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, urazole, the phonetic heavy stone used as an anchor of thiocarbamide, mercaptoimidazole, mercaptopyrimidine; 1,1-dimethyl urea, 1, the carbamide compounds such as 3-dimethyl urea; Thiourea compound etc.
Closely sealed promotor can be used alone or combines multiple use, and its addition is preferably below 1 mass parts with respect to polymkeric substance 100 mass parts.
[single coating type horizontal alignment film]
By rod, be coated with, spin coating, flow coat, roller coat, slot coated, follow the spin coating of slot coated closely, ink jet method, the methods such as print process, the present composition described above (is for example coated to substrate, silicon/silicon dioxide is substrate coated, silicon nitride board, be coated with for example aluminium of metal, molybdenum, the substrate of chromium etc., glass substrate, quartz base plate, ito substrate etc.) or film (for example, tri acetyl cellulose (TAC) film, cyclo-olefin-polymer films, polyethylene terephthalate film, the resin moldings such as acrylic film) etc. upper and form and film, then, by heat dryings such as hot plate or baking ovens, can form film.
As the condition of heat drying, can adopt the Heating temperature and the heat-up time that are for example selected from 50～100 ℃ of temperature, the scope of 0.1～60 minute time.Are preferably above-mentioned Heating temperature and heat-up time 50～80 ℃ and 0.1～2 minute.
The film forming is like this by carrying out linear polarization irradiation, and carries out rear baking, can obtain single coating type horizontal alignment film.
As the illuminating method of linear polarization, conventionally can, by using ultraviolet ray～visible ray of wavelength 150～450nm, under room temperature or heating condition, irradiate linear polarization and carry out.
In addition, rear baking is so long as heat by hot plate or baking oven etc., and its temperature and time is preferably 90～150 ℃ and 2～20 minutes, more preferably 95～120 ℃ and 5～20 minutes.
The thickness of single coating type horizontal alignment film of the present invention can consider the difference of height of used substrate and/or optics, electrical properties and suitable selection is for example suitably 0.1～3 μ m.
The single coating type horizontal alignment film of the present invention obtaining is like this material with the optical characteristics of the purposes that is suitable for display unit or recording materials etc., is particularly suitable as the optical compensation films of Polarizer that liquid-crystal display uses and polarizer etc.
Embodiment
Below, enumerate synthesis example, embodiment and comparative example, be described more specifically the present invention, still, the present invention is not subject to the restriction of following embodiment.Be explained, in an embodiment, measuring method and the condition determination of each physical property are as described below.
[1]NMR
Make compound be dissolved in deuterochloroform (CDCl 3), use nuclear magnetic resonance device (300MHz, ジオール society system), measure 1h-NMR.
[2] mean molecule flow measurement
Use the Shodex GPC-101 (solvent: tetrahydrofuran (THF), inspection amount line: polystyrene standard), measure number-average molecular weight (Mn), weight-average molecular weight (Mw) of clear and electrician's (strain) system.
[3] haze value
Use the Spectral Haze Meter (TC-1800H) of Tokyo electricity Se company limited system, measure the haze value of film.
[4] length of delay of film
Use length of delay determinator (RETS-100, large tomb electronics (strain) system), measure the length of delay of wavelength 550nm.
[5] polarized light microscope observing
Use the polarizing microscope E600-Pol of (strain) Nikon system to observe.
Synthesizing of [synthesis example 1] polymerizable compound (M1)
[changing 19]
Make 4-(6-acryloxy-1-hexyloxy) phenylformic acid (SYNTHON Chemicals company system) 29.2g (100mmol), 4-xenol 17.0g (100mmol), DMAP 0.6g and a small amount of butylated hydroxytoluene (BHT) under stirring at room, be suspended in methylene dichloride 200mL, add wherein the solution that DCC24.0g (116mmol) is dissolved in to methylene dichloride 100mL and obtains, stirring is spent the night.The DCC urea that filtration is separated out, this filtrate is respectively washed 2 times with 0.5mol/L hydrochloric acid 150mL, saturated sodium bicarbonate aqueous solution 150mL, saturated aqueous common salt 150mL successively, with after dried over mgso, distillation is except desolventizing, by refining with ethyl alcohol recrystallization, obtain target polymerization compound (M1) 39.6g (yield 89%).The measurement result of NMR is as follows.
1H-NMR(CDCl 3)δ：1.57(m，4H)，1.70(m，2H)，1.86(m，2H)，4.00(m，2H)，4.19(m，2H)，5.82(m，1H)，6.12(m，1H)，6.39(m，1H)，6.97(d，2H)，7.29(m，2H)，7.36(m，1H)，7.47(m，2H)，7.62(m，4H)，8.18(m，2H)
Synthesizing of [embodiment 1] polymerizable compound (M2)
(1) midbody compound (P2) is synthetic
[changing 20]
In the 500mL eggplant-shape bottle with prolong, add xenol 18.6g (100mmol), 2-(the bromo-1-butyl of 4-)-1,3-dioxolane 10.0g (48mmol), salt of wormwood 13.8g (100mmol) and acetone 200mL, make mixture, at 64 ℃ of temperature, stir 24 hours, make its reaction simultaneously.After reaction finishes, reaction solution is injected in pure water 500mL, obtains white solid.By this solid and methanol mixed, to filter, and distill except desolventizing, result obtains white solid.Then, this solid is mixed with chloroform, filter, and distillation is except desolventizing, obtains white solid 7.2g.The result of measuring this solid with NMR is as follows.By this results verification, this white solid is midbody compound (P2) (yield 48%).
1H-NMR(CDCl 3)δ：1.62(m，2H)，1.76(m，2H)，1.87(m，2H)，3.85(m，2H)，4.00(m，4H)，4.90(m，1H)，6.87(m，4H)，7.42(m，4H)
(2) midbody compound (Z2) is synthetic
[changing 21]
Then, in the 300mL eggplant-shape bottle with prolong, add midbody compound obtained above (P2) 7.2g (23mmol), 2-(brooethyl) vinylformic acid 4.1g (25mmol), THF60mL, tin chloride (II) 4.7g (25mmol) and 10 quality %HCl aqueous solution 19mL, make mixture, under temperature 70 C, stir and within 5 hours, make its reaction.After reaction finishes, reaction solution is injected in pure water 200mL, obtains white solid 6.1g.The result of being measured this solid by NMR is as follows.By this results verification, this white solid is midbody compound (Z2) (yield 78%).
1H-NMR(CDCl 3)δ：1.60-1.95(m，6H)，2.64(m，1H)，3.11(s，1H)，4.02(t，2H)，4.60(m，1H)，4.82(s，1H)，5.64(s，1H)，6.24(s，1H)，6.88(d，2H)，6.94(d，2H)，7.44(m，4H)
(3) polymerizable compound (M2) is synthetic
[changing 22]
Make compound (Z2) 3.4g (10mmol), 4-methoxy cinnamic acid 1.8g (10mmol), DMAP 0.08g and a small amount of BHT under stirring at room, be suspended in methylene dichloride 30mL, add wherein the solution that DCC2.6g (13mmol) is dissolved in to methylene dichloride 15mL and obtains, stirring is spent the night.The DCC urea that filtration is separated out, this filtrate is respectively washed 2 times with 0.5mol/L hydrochloric acid 50mL, saturated sodium bicarbonate aqueous solution 50mL, saturated aqueous common salt 50mL successively, with after dried over mgso, distillation is except desolventizing, by refining with ethyl alcohol recrystallization, obtain target polymerization compound (M2) 4.3g (yield 86%).The measurement result of NMR is below shown.
1H-NMR(CDCl 3)δ：1.60-1.90(m，6H)，2.63(m，1H)，3.09(m，1H)，3.87(s，3H)，4.03(m，2H)，4.57(m，1H)，5.64(m，1H)，6.24(d，1H)，6.54(d，1H)，6.95(m，4H)，7.26(m，2H)，7.44(m，2H)，7.57(m，4H)，7.86(d，1H)
Synthesizing of [synthesis example 2] polymerizable compound (M3)
[changing 23]
Make compound (Z3) (Midori chemistry (strain) system) 3.1g (10.0mmol), 4-methoxy cinnamic acid 1.8g (10.0mmol), DMAP 0.08g and a small amount of BHT under stirring at room, be suspended in methylene dichloride 30mL, add wherein the solution that DCC2.6g (12.5mmol) is dissolved in to methylene dichloride 15mL and obtains, stirring is spent the night.The DCC urea that filtration is separated out, this filtrate is respectively washed 2 times with 0.5mol/L hydrochloric acid 50mL, saturated sodium bicarbonate aqueous solution 50mL, saturated aqueous common salt 50mL successively, with after dried over mgso, distillation is except desolventizing, by refining with ethyl alcohol recrystallization, obtain target polymerization compound (M3) 3.4g (yield 72%).The measurement result of NMR is below shown.
1H-NMR(CDCl 3)δ：1.93(m，4H)，3.87(s，3H)，4.03(m，2H)，4.26(m，2H)，5.85(m，1H)，6.14(m，1H)，6.17(d，1H)，6.44(d，1H)，6.95(m，4H)，7.19(m，2H)，7.55(m，6H)，7.82(d，1H)
Synthesizing of [synthesis example 3] polymerizable compound (M4)
[changing 24]
Make 4-(6-acryloxy-1-hexyloxy) phenylformic acid (SYNTHON Chemicals company system) 29.2g (100mmol), 4-methoxyphenol 12.4g (100mmol), DMAP 0.8g and a small amount of BHT under stirring at room, be suspended in methylene dichloride 200mL, add wherein the solution that DCC24.0g (116mmol) is dissolved in to methylene dichloride 100mL and obtains, stirring is spent the night.The DCC urea that filtration is separated out, this filtrate is respectively washed 2 times with 0.5mol/L hydrochloric acid 150mL, saturated sodium bicarbonate aqueous solution 150mL, saturated aqueous common salt 150mL successively, with after dried over mgso, distillation is except desolventizing, by refining with ethyl alcohol recrystallization, obtain target polymerization compound (M4) 21.5g (yield 54%).The measurement result of NMR is below shown.
1H-NMR(CDCl 3)δ：1.57(m，4H)，1.70(m，2H)，1.86(m，2H)，3.82(s，3H)，4.00(m，2H)，4.19(m，2H)，5.84(m，1H)，6.13(m，1H)，6.39(m，1H)，6.97(m，4H)，7.10(m，2H)，8.1l(m，2H)
Synthesizing of [synthesis example 4] polymerizable compound (M5)
[changing 25]
Make 4-(6-acryloxy-1-hexyloxy) phenylformic acid (SYNTHON Chemicals company system) 14.6g (50mmol), 4-cyanophenol 5.9g (50mmol), DMAP 0.4g and a small amount of BHT under stirring at room, be suspended in methylene dichloride 100mL, add wherein the solution that DCC12.0g (58mmol) is dissolved in to methylene dichloride 50mL and obtains, stirring is spent the night.The DCC urea that filtration is separated out, this filtrate is respectively washed 2 times with 0.5mol/L hydrochloric acid 100mL, saturated sodium bicarbonate aqueous solution 100mL, saturated aqueous common salt 100mL successively, with after dried over mgso, distillation is except desolventizing, by refining with ethyl alcohol recrystallization, obtain target polymerization compound (M5) 14.5g (yield 74%).The measurement result of NMR is below shown.
1H-NMR(CDCl 3)δ：1.57(m，4H)，1.71(m，2H)，1.86(m，2H)，4.00(m，2H)，4.19(m，2H)，5.84(m，1H)，6.13(m，1H)，6.39(m，1H)，6.99(m，2H)，7.36(m，2H)，7.72(m，2H)，8.1l(m，2H)
Synthesizing of [embodiment 2] polymkeric substance (1)
[changing 26]
In possessing the flask of prolong, pack polymerizable compound (M1) 0.62g (1.4mmol), polymerizable compound (M2) 0.30g (0.6mmol), NMP8.3g and the AIBN17mg that embodiment 1 obtains that synthesis example 1 obtains into, to in flask, be replaced into after nitrogen, under temperature 60 C, stir and within 20 hours, make its reaction.The reaction soln obtaining is put in 200mL methyl alcohol, made white powder precipitation.After this white powder is filtered, at room temperature carry out vacuum-drying, obtain polymkeric substance (1) 0.65g (yield 71%).
The Mn of resulting polymers (1) is that 10975, Mw is 19206 (Mw/Mn=1.75).
Synthesizing of [comparative example 1] polymkeric substance (2)
[changing 27]
In possessing the flask of prolong, pack polymerizable compound (M1) 0.62g (1.4mmol), polymerizable compound (M3) 0.28g (0.6mmol), NMP9.0g and the AIBN17mg that synthesis example 2 obtains that synthesis example 1 obtains into, to in flask, be replaced into after nitrogen, under temperature 60 C, stir and within 20 hours, make its reaction.The reaction soln obtaining is put in 200mL methyl alcohol, made white powder precipitation.After this white powder is filtered, at room temperature carry out vacuum-drying, obtain polymkeric substance (2) 0.67g (yield 74%).
The Mn of resulting polymers (2) is that 7068, Mw is 9542 (Mw/Mn=1.35).
Synthesizing of [embodiment 3] polymkeric substance (3)
[changing 28]
In possessing the flask of prolong, pack polymerizable compound (M1) 0.44g (1.0mmol), polymerizable compound (M2) 0.30g (0.6mmol), n-BMA 0.06g (0.4mmol), NMP7.2g and the AIBN17mg that embodiment 1 obtains that synthesis example 1 obtains into, to in flask, be replaced into after nitrogen, under temperature 60 C, stir and within 20 hours, make its reaction.The reaction soln obtaining is put in 200mL methyl alcohol, made white powder precipitation.After this white powder is filtered, at room temperature carry out vacuum-drying, obtain polymkeric substance (3) 0.71g (yield 89%).
The Mn of resulting polymers is that 12664, Mw is 39258 (Mw/Mn=3.10).
Synthesizing of [embodiment 4] polymkeric substance (4)
[changing 29]
In possessing the flask of prolong, pack polymerizable compound (M1) 0.44g (1.0mmol), polymerizable compound (M2) 0.30g (0.6mmol), 2-EHA 0.07g (0.4mmol), NMP8.0g and the AIBN17mg that embodiment 1 obtains that synthesis example 1 obtains into, to in flask, be replaced into after nitrogen, under temperature 60 C, stir and within 20 hours, make its reaction.The reaction soln obtaining is put in 200mL methyl alcohol, made white powder precipitation.After this white powder is filtered, at room temperature carry out vacuum-drying, obtain polymkeric substance (4) 0.54g (yield 67%).
The Mn of resulting polymers is that 10357, Mw is 23925 (Mw/Mn=2.31).
Synthesizing of [embodiment 5] polymkeric substance (5)
[changing 30]
In possessing the flask of prolong, pack polymerizable compound (M1) 0.36g (0.8mmol), polymerizable compound (M2) 0.30g (0.6mmol), 2-EHA 0.11g (0.6mmol), NMP7.0g and the AIBN17mg that embodiment 1 obtains that synthesis example 1 obtains into, to in flask, be replaced into after nitrogen, under temperature 60 C, stir and within 20 hours, make its reaction.The reaction soln obtaining is put in 200mL methyl alcohol, made white powder precipitation.After this white powder is filtered, at room temperature carry out vacuum-drying, obtain polymkeric substance (5) 0.45g (yield 58%).
The Mn of resulting polymers is that 11065, Mw is 28769 (Mw/Mn=2.6).
Synthesizing of [embodiment 6] polymkeric substance (6)
[changing 31]
In possessing the flask of prolong, pack polymerizable compound (M1) 0.44g (1.0mmol), polymerizable compound (M2) 0.30g (0.6mmol), vinylformic acid dodecyl ester 0.10g (0.4mmol), NMP8.0g and the AIBN17mg that embodiment 1 obtains that synthesis example 1 obtains into, to in flask, be replaced into after nitrogen, under temperature 60 C, stir and within 20 hours, make its reaction.The reaction soln obtaining is put in 200mL methyl alcohol, made white powder precipitation.After this white powder is filtered, at room temperature carry out vacuum-drying, obtain polymkeric substance (6) 0.60g (yield 71%).
The Mn of resulting polymers is that 10828, Mw is 23822 (Mw/Mn=2.2).
Synthesizing of [embodiment 7] polymkeric substance (7)
[changing 32]
In possessing the flask of prolong, pack polymerizable compound (M1) 0.36g (0.8mmol), polymerizable compound (M2) 0.30g (0.6mmol), vinylformic acid dodecyl ester 0.14g (0.6mmol), NMP8.0g and the AIBN17mg that embodiment 1 obtains that synthesis example 1 obtains into, to in flask, be replaced into after nitrogen, under temperature 60 C, stir and within 20 hours, make its reaction.The reaction soln obtaining is put in 200mL methyl alcohol, made white powder precipitation.After this white powder is filtered, at room temperature carry out vacuum-drying, obtain polymkeric substance (7) 0.50g (yield 63%).
The Mn of resulting polymers is that 12455, Mw is 22544 (Mw/Mn=1.81).
Synthesizing of [comparative example 2] polymkeric substance (8)
[changing 33]
In possessing the flask of prolong, pack polymerizable compound (M1) 0.44g (1.0mmol), polymerizable compound (M3) 0.28g (0.6mmol), vinylformic acid dodecyl ester 0.10g (0.4mmol), NMP8.2g and the AIBN17mg that synthesis example 2 obtains that synthesis example 1 obtains into, to in flask, be replaced into after nitrogen, under temperature 60 C, stir and within 20 hours, make its reaction.The reaction soln obtaining is put in 200mL methyl alcohol, made white powder precipitation.After this white powder is filtered, at room temperature carry out vacuum-drying, obtain polymkeric substance (8) 0.58g (yield 71%).
The Mn of resulting polymers is that 8025, Mw is 11556 (Mw/Mn=1.44).
Synthesizing of [embodiment 8] polymkeric substance (9)
[changing 34]
In possessing the flask of prolong, pack polymerizable compound (M5) 0.55g (1.4mmol), polymerizable compound (M2) 0.30g (0.6mmol), NMP8.0g and the AIBN17mg that embodiment 1 obtains that synthesis example 4 obtains into, to in flask, be replaced into after nitrogen, under temperature 60 C, stir and within 20 hours, make its reaction.The reaction soln obtaining is put in 200mL methyl alcohol, made white powder precipitation.After this white powder is filtered, at room temperature carry out vacuum-drying, obtain polymkeric substance (9) 0.60g (yield 71%).
The Mn of resulting polymers (9) is that 15269, Mw is 24430 (Mw/Mn=1.60).
Synthesizing of [embodiment 9] polymkeric substance (10)
[changing 35]
In possessing the flask of prolong, pack polymerizable compound (M5) 0.39g (1.0mmol), polymerizable compound (M2) 0.30g (0.6mmol), vinylformic acid dodecyl ester 0.10g (0.4mmol), NMP8.0g and the AIBN17mg that embodiment 1 obtains that synthesis example 4 obtains into, to in flask, be replaced into after nitrogen, under temperature 60 C, stir and within 20 hours, make its reaction.The reaction soln obtaining is put in 200mL methyl alcohol, made white powder precipitation.After this white powder is filtered, at room temperature carry out vacuum-drying, obtain polymkeric substance (10) 0.55g (yield 69%).
The Mn of resulting polymers is that 15040, Mw is 35795 (Mw/Mn=2.38).
Synthesizing of [embodiment 10] polymkeric substance (11)
[changing 36]
In possessing the flask of prolong, pack polymerizable compound (M4) 0.40g (1.0mmol), polymerizable compound (M2) 0.30g (0.6mmol), vinylformic acid dodecyl ester 0.10g (0.4mmol), NMP8.0g and the AIBN17mg that embodiment 1 obtains that synthesis example 3 obtains into, to in flask, be replaced into after nitrogen, under temperature 60 C, stir and within 20 hours, make its reaction.The reaction soln obtaining is put in 200mL methyl alcohol, made white powder precipitation.After this white powder is filtered, at room temperature carry out vacuum-drying, obtain polymkeric substance (11) 0.55g (yield 69%).
The Mn of resulting polymers is that 11873, Mw is 26358 (Mw/Mn=2.22).
[preparation of composition and the making of film and evaluation]
With the polymkeric substance obtaining in above-described embodiment, comparative example, prepare composition, according to following condition, make film, and inquire into its characteristic.
The manufacturing conditions of film:
Spin coating: 300rpm/5 second, 800～2000rpm/20 second
Preliminary drying: 50 ℃/20 seconds (hot-plate)
Exposure: linear polarization ultraviolet ray, wavelength 313nm, vertical irradiation, roentgen dose X 500mJ/cm 2
Rear baking: 100 ℃/10 minutes (hot-plate)
[embodiment 11]
Polymkeric substance (1) 150mg and surfactant R-30 (DIC (strain) system) 0.3mg is dissolved in pimelinketone 850mg, obtains the solution of polymkeric substance (1).
By spin coating by this solution coat on glass substrate, after preliminary drying, let cool to room temperature.Now, the film obtaining on substrate is transparent.
Then, make to be formed on the exposure of filming on glass substrate, then carry out rear baking.The thickness of the film obtaining is 0.8 μ m, with polarizing microscope, it observed, and results verification, film is horizontal alignment with respect to substrate surface.And its length of delay (Δ nd) is 62.3nm, haze value is 2.1%.
[comparative example 3]
Polymkeric substance (2) 150mg and surfactant R-30 (DIC (strain) system) 0.3mg is dissolved in pimelinketone 850mg, obtains the solution of polymkeric substance (2).
By spin coating by this solution coat on glass substrate, after preliminary drying, let cool to room temperature.Now, the film obtaining on substrate is transparent.
Then, make to be formed on the exposure of filming on glass substrate, then carry out rear baking.The thickness of the film obtaining is 0.7 μ m, with polarizing microscope, it is observed, and result, cannot obtain horizontal alignment film, and its Δ nd is 7.6nm, and haze value is 10.5%.
[embodiment 12]
Polymkeric substance (3) 150mg and surfactant R-30 (DIC (strain) system) 0.3mg is dissolved in pimelinketone 850mg, obtains the solution of polymkeric substance (3).
By spin coating by this solution coat on glass substrate, after preliminary drying, let cool to room temperature.Now, the film obtaining on substrate is transparent.
Then, make to be formed on the exposure of filming on glass substrate, then carry out rear baking.The thickness of the film obtaining is 0.8 μ m, with polarizing microscope, it observed, and results verification, film is horizontal alignment with respect to substrate surface.And its Δ nd is 96.7nm, haze value is 1.3%.
[embodiment 13]
Polymkeric substance (4) 150mg and surfactant R-30 (DIC (strain) system) 0.3mg is dissolved in pimelinketone 850mg, obtains the solution of polymkeric substance (4).
By spin coating by this solution coat on glass substrate, after preliminary drying, let cool to room temperature.Now, the film obtaining on substrate is transparent.
Then, make to be formed on the exposure of filming on glass substrate, then carry out rear baking.The thickness of the film obtaining is 0.9 μ m, with polarizing microscope, it observed, and results verification, film is horizontal alignment with respect to substrate surface.And its Δ nd is 118.8nm, haze value is 0.9%.
[embodiment 14]
Polymkeric substance (5) 150mg and surfactant R-30 (DIC (strain) system) 0.3mg is dissolved in pimelinketone 850mg, obtains the solution of polymkeric substance (5).
By spin coating by this solution coat on glass substrate, after preliminary drying, let cool to room temperature.Now, the film obtaining on substrate is transparent.
Then, make to be formed on the exposure of filming on glass substrate, then carry out rear baking.The thickness of the film obtaining is 0.9 μ m, with polarizing microscope, it observed, and results verification, film is horizontal alignment with respect to substrate surface.And its Δ nd is 99.1nm, haze value is 0.4%.
[embodiment 15]
Polymkeric substance (6) 150mg and surfactant R-30 (DIC (strain) system) 0.3mg is dissolved in pimelinketone 850mg, obtains the solution of polymkeric substance (6).
By spin coating by this solution coat on glass substrate, after preliminary drying, let cool to room temperature.Now, the film obtaining on substrate is transparent.
Then, make to be formed on the exposure of filming on glass substrate, then carry out rear baking.The thickness of the film obtaining is 0.8 μ m, with polarizing microscope, it observed, and results verification, film is horizontal alignment with respect to substrate surface.And its Δ nd is 113.3nm, haze value is 0.9%.
[embodiment 16]
Polymkeric substance (7) 150mg and surfactant R-30 (DIC (strain) system) 0.3mg is dissolved in pimelinketone 850mg, obtains the solution of polymkeric substance (7).
By spin coating by this solution coat on glass substrate, after preliminary drying, let cool to room temperature.Now, the film obtaining on substrate is transparent.
Then, make to be formed on the exposure of filming on glass substrate, then carry out rear baking.The thickness of the film obtaining is 0.9 μ m, with polarizing microscope, it observed, and results verification, film is horizontal alignment with respect to substrate surface.And its Δ nd is 118.3nm, haze value is 1.8%.
[comparative example 4]
Polymkeric substance (8) 150mg and surfactant R-30 (DIC (strain) system) 0.3mg is dissolved in pimelinketone 850mg, obtains the solution of polymkeric substance (8).
By spin coating by this solution coat on glass substrate, after preliminary drying, let cool to room temperature.Now, the film obtaining on substrate is transparent.
Then, make to be formed on the exposure of filming on glass substrate, then carry out rear baking.The thickness of the film obtaining is 0.8 μ m, with polarizing microscope, it is observed, and result, cannot obtain horizontal alignment film, and its Δ nd is 8.4nm, and haze value is 4.7%.
[embodiment 17]
Polymkeric substance (9) 150mg and surfactant R-30 (DIC (strain) system) 0.3mg is dissolved in pimelinketone 850mg, obtains the solution of polymkeric substance (9).
By spin coating by this solution coat on glass substrate, after preliminary drying, let cool to room temperature.Now, the film obtaining on substrate is transparent.
Then, make to be formed on the exposure of filming on glass substrate, then carry out rear baking.The thickness of the film obtaining is 0.8 μ m, with polarizing microscope, it observed, and results verification, film is horizontal alignment with respect to substrate surface.And its Δ nd is 86.0nm, haze value is 2.2%.
[embodiment 18]
Polymkeric substance (10) 150mg and surfactant R-30 (DIC (strain) system) 0.3mg is dissolved in pimelinketone/toluene (mass ratio 25/75) 850mg, obtains the solution of polymkeric substance (10).
By spin coating by this solution coat on glass substrate, after preliminary drying, let cool to room temperature.Now, the film obtaining on substrate is transparent.
Then, make to be formed on the exposure of filming on glass substrate, then carry out rear baking.The thickness of the film obtaining is 1.0 μ m, with polarizing microscope, it observed, and results verification, film is horizontal alignment with respect to substrate surface.And its Δ nd is 77.3nm, haze value is 0.5%.
[embodiment 19]
Make polymkeric substance (11) 150mg and surfactant R-30 (DIC (strain) system) 0.3mg be dissolved in pimelinketone/toluene (mass ratio 25/75) 850mg, obtain the solution of polymkeric substance (11).
By spin coating by this solution coat on glass substrate, after preliminary drying, let cool to room temperature.Now, the film obtaining on substrate is transparent.
Then, make to be formed on the exposure of filming on glass substrate, then carry out rear baking.The thickness of the film obtaining is 0.9 μ m, with polarizing microscope, it observed, and results verification, film is horizontal alignment with respect to substrate surface.And its Δ nd is 76.2nm, haze value is 0.5%.
To the results are summarized in above following table 1.
[table 1]
? Polymkeric substance Thickness (μ m) Δnd(nm) Haze value (%) Δn
Embodiment 11 (1) 0.8 62.3 2.1 0.08
Comparative example 3 (2) 0.7 7.6 10.5 0.01
Embodiment 12 (3) 0.8 96.7 1.3 0.12
Embodiment 13 (4) 0.9 118.8 0.9 0.13
Embodiment 14 (5) 0.9 99.1 0.4 0.11
Embodiment 15 (6) 0.8 113.3 0.9 0.14
Embodiment 16 (7) 0.9 118.3 1.8 0.13
Comparative example 4 (8) 0.8 8.4 4.7 0.01
Embodiment 17 (9) 0.8 86.0 2.2 0.11
Embodiment 18 (10) 1.0 77.3 0.5 0.08
Embodiment 19 (11) 0.9 76.2 0.5 0.08
Fig. 1 and Fig. 2 represent the dependence of angle of the length of delay (Δ nd) of embodiment 11～16 and comparative example 3 and 4 made films.Known when embodiment 11～16 (Fig. 1) is compared with comparative example 3 and 4 (Fig. 2), in embodiment 11～16, demonstrate horizontal alignment, in contrast to this, in comparative example 3 and 4, do not demonstrate horizontal alignment completely, Δ nd is also lower.

Claims (9)

1. polymkeric substance, is characterized in that, the repeating unit that contains following formula [1a], [1b] and [1c] expression,
In formula, X and Y are the group that following formula [2] or [3] represent independently of one another,
In formula [3], R 1for hydrogen atom or methyl, dotted line is key,
M 1for the group that following formula [4] represents, M 2for the group of following formula [5] expression,
In formula [4] and [5], s1, s2, s3 and s4 are 1 or 2, G independently of one another 1and G 2be independently of one another singly-bound ,-COO-or-OCO-, R 2and R 3be the alkyl of hydrogen atom, halogen atom, cyano group, carbon number 1～10 or the alkoxyl group of carbon number 1～10 independently of one another, dotted line is key,
A is the straight or branched alkyl of carbon number 2～15,
M, n and p are respectively the number that meets 0<m<1,0<n<1,0≤p≤0.5 and m+n+p≤1,
Q and r are 2～9 integer independently of one another.
2. polymkeric substance claimed in claim 1, wherein, above-mentioned X and Y are the group that above-mentioned formula [3] represents.
3. the polymkeric substance described in claim 1 or 2, wherein, above-mentioned m, n and p are respectively the number that meets 0.2≤m≤0.9,0.1≤n≤0.8,0≤p≤0.4.
4. polymkeric substance claimed in claim 3, wherein, above-mentioned m, n and p are respectively the number that meets 0.2≤m≤0.8,0.1≤n≤0.5,0.1≤p≤0.3.
5. composition, contains polymkeric substance and organic solvent described in claim 1～4 any one.
6. single coating type horizontal alignment film, it is by composition claimed in claim 5 is coated on substrate, then irradiates polarisation and it is solidified obtain.
7. single coating type horizontal alignment film claimed in claim 6, wherein, above-mentioned polarisation is linear polarization ultraviolet ray.
8. optics, it possesses the single coating type horizontal alignment film described in claim 6 or 7.
9. polymerizable compound, is characterized in that, by following formula [7], represented,
In formula [7], s3 and s4 are 1 or 2, G independently of one another 2for singly-bound ,-COO-or-OCO-, R 3for the alkyl of hydrogen atom, halogen atom, cyano group, carbon number 1～10 or the alkoxyl group of carbon number 1～10.
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* Cited by examiner, † Cited by third party
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102159560A (en) * 2008-10-14 2011-08-17 日产化学工业株式会社 Polymerizable liquid crystal compound, polymerizable liquid crystal composition and oriented film
CN102630225A (en) * 2009-09-16 2012-08-08 日产化学工业株式会社 Polymerizable liquid crystal compound, polymerizable liquid crystal composition, and oriented film

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6270407A (en) 1985-09-25 1987-03-31 Fuji Photo Film Co Ltd Preparation of orientated film
JPH09208957A (en) 1996-01-31 1997-08-12 Teijin Ltd Production of optical isomer
JP3945790B2 (en) 1997-12-25 2007-07-18 林テレンプ株式会社 Birefringent film and manufacturing method thereof
GB9812636D0 (en) 1998-06-11 1998-08-12 Rolic Ag Optical component orientation layer and layerable polymerisable mixture
JP5062419B2 (en) * 2005-04-20 2012-10-31 日産化学工業株式会社 Polymerizable liquid crystal compound, polymerizable liquid crystal composition containing the same, and polymer obtained using the same
ES2494293T3 (en) 2006-09-13 2014-09-15 Rolic Ag Photoaligned Volume Retarder
KR101466603B1 (en) * 2006-12-15 2014-11-28 닛산 가가쿠 고교 가부시키 가이샤 Polymerizable liquid crystal compound, polymerizable liquid crystal composition, and alignment film
JP2008164925A (en) 2006-12-28 2008-07-17 Hayashi Telempu Co Ltd Retardation film and method for producing the same
WO2012077600A1 (en) * 2010-12-07 2012-06-14 日産化学工業株式会社 Polymerizable compound, polymerizable liquid crystal composition, polymer and alignment film

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102159560A (en) * 2008-10-14 2011-08-17 日产化学工业株式会社 Polymerizable liquid crystal compound, polymerizable liquid crystal composition and oriented film
CN102630225A (en) * 2009-09-16 2012-08-08 日产化学工业株式会社 Polymerizable liquid crystal compound, polymerizable liquid crystal composition, and oriented film

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105051104A (en) * 2013-03-15 2015-11-11 日产化学工业株式会社 Composition and single-coat type film with horizontal alignment
CN105051104B (en) * 2013-03-15 2017-04-05 日产化学工业株式会社 Compositionss and single coating type horizontal alignment film
CN108884391A (en) * 2016-02-10 2018-11-23 日产化学株式会社 Liquid-crystal composition and single coating type horizontal alignment film
CN108884391B (en) * 2016-02-10 2022-06-10 日产化学株式会社 Liquid crystal composition and single-layer coating type horizontal alignment film
CN109923449A (en) * 2016-08-31 2019-06-21 日产化学株式会社 Phase difference film and its manufacturing method with water vapor barrier property
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CN113544554A (en) * 2019-03-07 2021-10-22 富士胶片株式会社 Polarizing element and image display device

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